New Protective Groups, Afffinity or "Handle" isolation techniques, and amide forming reagents are sought that can improve the versatility, scope, and reliability of existing methods of peptide synthesis. We have recently reported progress toward realization of a strategy of peptide bond formation involving prior capture of the thiol function of peptide amine component that bears an N-terminal cysteine residue. Further work is in progress involving refinement of model structures, acylation mechanism, and capture chemistry, with the objective developing a practical thiol capture system that can be applied to synthesis and semisynthesis of large peptide residues.